Process for reacting an alkylated indene with a phenolic compound



Patented June 29, 1948 UNITED, STATES PATENT OFFICE.

PROCESS FOR REACTING AN ALKYLATED INDENE WITH, A PHENOLIC COMROUND Frank J. Soday, Baton Rouge, La., alsignor to The United Gas Improvement Company, a corporaflon of Pennsylvania No Drawing. Application February 9, 1944, Serial No. 521,112

2 Claims. (Cl. 260-819) This invention pertains generally to a process for the production of reaction products of a substituted indene type compound and a phenol, and pertains particularly to the production of substituted indene phenol.

The invention pertains more particularly to the production of compounds of this type capable of being further reacted with aldehydes generally to obtain resins or the phenol-aldehyde type which the liquid coating composition field.

Since the more common phenol-aldehyde resins are not soluble in drying oils to a satisfactory degree, the use of such resins in the liquid coating composition field is limited.

However, after having acquired the quality of unusual oil solubility, the field of use of resins of the phenol-aldehyde type is greatly extended.

Ihave discovered that substituted indene-phenol type compounds generally and substituted indene phenol particularly may be produced with high yields of excellent quality by reacting a hydrohalide of substituted indene with a phenol in the presence of a suitable catalyst.-

In addition to pure substituted indene, commercial and technical grades thereof, I may also employ fractions and/or mixtures containing any desired proportion of substituted indene in the I practice of my invention.

fractions boiling mainly in the range of 190 to,

For certain purposes, the use of narrower boiling fractions may be desirable. Thus, I have found that particularly desirable substituted phenols of the type described herein are obtained when substituted indene fractions boiling mainly in the range of, (a) 190 to 200 C.. (b) 200 to 210 'C., and/or (3) 210 to 220 C. are employed, Extensive investigation has indicated that the -2 predominating unsaturatedhydrocarbons present in such fractions are one or more methyl substituted indenes.

The substituted indenes which may be employed in the practice of my invention may be represented by the following structural formula in which at least one of the group consisting of R1 to Re, inclusive, is an alkyl group, such as, methyl, ethyl, propyl, isopropyl, butyl, lsobutyl, amyl, the remainder being hydrogen.

The use of the methyl-substituted indenes is preferred for the uses disclosed herein. Excellent results are obtained by the use of one or more methyl indenes.

Mono-alkyl substituted indenes are irequently preferred, particularly when the alkyl group contains less than 6 carbon atoms, for example, monomethyl substituted indene.

While substituted indene fractions containing almost any desired proportion of substituted indene may be used in the practice of my invention, I prefer to employ light oil substituted indene fractions containing at least 20% substituted indene and more particularly at least 30% substituted indene. Excellent results'are obtained by the use of fractions containing at least 40% substituted indene.

Excellent results are obtained by the use of fractions containing from 15 to substituted indenes.

Examples of phenols are phenol itself, other mono or poly-valent phenols, their substitution products such as the halogen, sulfo, alkyl, aryl, a'ralkyl, nitro, carboxyl, and azo-nuclear substitution products, and phenolic compounds in general. Within this class of compounds are included cresol, amino-phenols, nitro-phenols. chloro-phenols, thymol, naphthols, pyrocatechol, resorcinol, hydroquinone, pyrogallol, oxyhydroquinone, phloroglucinol, carvacrol, quinol, xylenol, guaiacol, orcinol, mesitol, pseudocumenol, toluhydroquinone, alpha naphthol, and beta naphthol, as well as mixtures containing one or more of these compounds.

Low temperature tar phenols and mixtures of -phenolic compounds also may be used. These are contained, for example, in tar oils or alcohols, such as benzyl alcohol, or acids, such as acetic acid. The phenolic compounds may be used in the pure state, or as crude materials, or as technical mixtures.

Phenolic others also may be used in the process.

A compound of the foregoing character will be referred to in the claims as a phenol.

In carrying out the reaction between a substituted indene hydrohalide and a phenol, I prefer to employ as a catalyst one or more metal halides which term includes the boron halides and the complexes of all of the foregoing halides, and particularly the organic solvent complexes of said halides.

Examples of metal halides are aluminum chloride, zinc chloride, ferric chloride, boron trifluoride, boron trichloride, aluminum bromide, stannic chloride, titanium chloride, antimony bromide, and antimony chloride. These compounds and complexes thereof are members of a group which for convenience may be designated as acidacting metal halides. The reaction products resulting from the addition of these halides to diethyl ether may be regarded as examples of acidacting metal halide-organic solvent complexes, though complexes are formed with many other organic solvents as well as other materials as is well known in the art.

Other catalysts which might be employed are the metal oxides such as aluminum oxide, thorium oxide, tungstic oxide, and phosphoric anhydride; metal salts, such as potassium bisulphate, aluminum sulfate, aluminum phosphate, and aluminum silicate and contact substances, such as silica gel, alumina, tonsil, kaolin, activated charcoal, clay, kieselguhr, diatomaceous earth, fullers earth, silicious earths, and metallic hydrosilicates.

Catalysts may be employed singly or in mixtures with each other and may or may not be deposited on carriers, such as the previously listed contact materials or other substances such as barium sulfate, pumice, asbestos and silica. The substituted indene hydrohalide to be used as starting material may be obtained from any suitable source known in .the art, or may be prepared for instance, by the addition of a selected hydrogen halide, such as hydrogen chloride, to substituted indene.

In case the substituted indene hydrohalide is to be prepared, the substituted indene to be hydrohalogen'ated may be either in concentrated form or in the form of a fraction or solution.

-For example, substituted indene may be be obtained from light oil produced in the manufacture of gas, such as carburetted water gas or oil gas. The concentration ofsubstltuted indene in a fraction is frequently relatively low, particularly in the case of forerunnings, and afterrunnings, due to the difiiculty of concentrating by distillation compounds which are capable of being polymerized by heat.

' All of such fractions lend themselves to the production of substituted indene hydrohalides.

The substituted indene hydrohalides may be separated from such fractions, say by distillation, or may be employed without such separation.

As a general rule, the isomeric substitutedindene hydrohalides are produced in this way.

However, the reaction might be carried out in a manner such that one or the other form predominates.

If desired, the isomeric compounds may be separated prior to their reaction with the phenol, or they may be reacted with the phenol without previous separation.

There are several possible reactions between a 4 chloride and phenol presumably takes place in the following manner.

e Catalyst Substituted indene hydrohalide Phenol O p-Substituted indene phenol HCl The product shown represents the para substitution product.

From theoretical considerations, the ortho compound also may be formed in the same reaction Presumably very little, if any, meta substituted compound is formed.

The isomeric substituted indene hydrohalide also may react with phenolic compounds in a similar manner.

H Catalyst Substituted indene Phenol hydrohalide \/-H OH p-Substituted indene phenol The product shown in Reaction 3 is the para substituted form.

The ortho substituted form also may be formed in this reaction as shown in the following equation. 4 0H r R \/L Catalyst Substituted indene Phenol hydrohalide R- El 01 o-Substituted indene phenol a Presumably very little, if any, meta substituted compound is formed.

The reaction between a. substituted indene hydrohalide and a phenol may also result in the production of diand poly-substituted derivatives, as shown, for example, by the following equation.

Catalyst p-Substituted indene phenol n mod no, p-Substituted indene phenol In addition, substituted indene hydrohalides may react with phenolic compounds to give phe- Substituted indene hydrohalide nolic ethers, as shown in the following equation.

Substituted indene Phenol Substituted indene phenyl ether the diand poly-substituted derivatives. it is possible to vary the proportion" of one to the other by varying the proportion of starting materials.

For example, when phenol is in excess, substituted indene phenol predominates in the reaction product, while when substituted indene hydrohalide is in excess the reaction product contains larger quantities of diand poly-substituted indene phenols.

In carrying out my invention, the reactants may be combined in any desired manner whether or not in concentrated form, or in solution or admixture.

. Contact between the materials may be effected in any manner known in the art. In this connection, reference is had to the very large num- 6 1 tion at moderate temperatures, for example, between 0 and 100 0., followed by higher temperatures, such as between 100 and 220 C.

Temperatures between 40 and 55 C. for the initial reaction followed by temperatures between 140 and 150 C. for the final reaction, are found to be particularly suitable.

In case the temperature is held uniform, temperatures between 10 and 180 C. are preferred.

While the reaction is customarily carried out at atmospheric pressure, it will be understood that sub-atmospheric and super-atmospheric pressures may be employed if desired.

The quantity of catalysts employed may also be varied over fairly wide limits. As an example,

- 0.1% to 10% by weight of catalyst" to the combined weight of both reactants will be found suitable.

When using acid-acting metal halide catalysts which term as used herein includes complexes, 0.1% to 5% by weight of catalyst to the combined weight of both reactants is found particularly suitable.

In order to speed up the reaction and carry it further to completion, steps may be taken to remove hydrogen halide from the sphere of the reaction, such as by absorption, or by stirring or by passing an inert gas through the reaction mass.

The lwdrogen halide thus displaced from the reaction mass may, of course, be recovered and reused in the hydrohalogenation of substituted in- I dene.

However, considerable quantities of hydrogen halide escape from the reaction mass without external aid.

The following example will further illustrate the process.

- EXAMPLE 1 A light oil substituted indene fraction,- obtained by the fractionation of light oil obtained from oil gas and boiling mainly in the range of 190 to 200 C., and containing one mole of substituted indene, is placed in a one liter three-neck flask equipped with a stirring device. The flask and its contents are cooled to a temperature of 0 C. and a moderate stream of dry hydrogen chloride introduced into the flask. The reaction is continued for a her of different ways of contacting reactants in stituted indene hydrohalide and the catalyst.

, The reaction may be carried out at almost any desired temperature which may vary during the reaction.

.I find, for example, that excellent results are secured by conducting the first part of the reacperiod of 24 hours, during which time approximately the theoretical amount of hydrogen chloride to convert the substituted indene present to substituted indene hydrohalide is absorbed.

The excess hydrogen chloride is removed from the substituted indene fraction by distilling under reduced pressure. The residual material is washed with water, dried, and distilled in a Vigreux column to remove the unchanged hydrocarbons present. The residue then is fractionated.

The substitutedindene hydrohalide obtained is slowly added with good agitation to a, mixture of one mol grams of phenol, 3.0 grams of aluminum chloride, and 200 grams of freshly dried n-heptane. The reaction mixture is agitated for a period of 6 hours at room temperature, followed by agitation for an additional period ,of one hour at a temperature of 100 C. During the first hour of the reaction, considerable quantities of hydrogen chloride is given off by the reaction mixture.

The catalyst component of the mixture is neutralized with a 20% aqueous solution of sodium carbonate and washed with several-volumes of water. The product then is distilled under reduced pressure (4.5 mm.) in a Claissen flask. Approximately an yield of substituted indene 7 phenol boiling in the range of 150 to 200 C. 6 mm. is obtained. The product has a specific gravity (1220/4) of 1.075 and a refractive index (12 of 1.587.

Exmt: 2

This is a repetition of Example 1, with the exception that a light oil substituted indene fraction boiling mainly in the range of 200 to 210 C. is employed. The substituted indene phenol obtained boils mainly in the range of 160 to 205 C., has a density (D20/4) of 1.064, and a refractive index (1t of 1.583.

Exmta 3 I This was a repetition of Example '1, with the exception that alight oil methyl indene fraction the reaction mass to start the reaction, followed by the addition of the remainder of the substitutedindene; 1 V y On the other hand, hydrogen halide maybe :suppliedby bubbling it through the reaction mass. M f This is illustrated inExample 4.

Exsmra 4 A mixture of 340 grams of phenol, 2 grams'of an 80% substituted indene fraction (containing 1.7 grams of substituted indene) andl'I grams of aluminum chlorideis placed in a one-liter th'ree-' neck'flask' at room temperature. Gaseous hydrogen chlorideis passed through this'mixturefor a period of one minute, after which the, addition ofhydrogen chloride is discontinued. A 130 gram portionof the same substituted indene fraction "(containing 115' grams of substituted indene) is 'slowly added tothe mixture during a period of one hour. The mixture is continually agitated during this time and the temperatureis maintained within 40-55 Q. The temperature is raised to 140-150" C. during a period of 20 minutes, and maintained at this pointfor an additional period of 2 hours.

The catalyst component of the solution then is neutralized with a 20% solution or sodium carbonate containing 4 grams of Na2COa. The water layer is separated and the residue distilled in a modified Claissen flask under reduced pressure. An excellent obtained.

A further modification of this invention resides EXAMPLE 5 A very slightly moist substituted indene fraction obtained by the distillation of light oil from yield of substituted indene phenol is' oil gas,.and containing one mol of substituted indene is slowly added with good agitation to a mixture of one moi of phenol and 1.56 gram of aluminum chloride during a period of one hour at a temperature of 40-55" C. The temperature is raised to 140-450 C. during a period of '20 minutes, and the contents of the flask maintained at this temperature during an additional period of 2 hours.

The catalyst then is neutralized by the addition of sodium carbonate in the form of a solution. The residue then is distilled in a modified Ciaissen flask under reduced pressure.

Substituted indene phenol is obtained in an excellent yield.

The boiling range of the substituted indene phenols listed in the foregoing examples does not necessarily represent the true boiling range of the material due to excessive superheatin g during the distillation process.

The mechanism proposed for this reaction is of I the chain type. Substituted indene hydrohallde reacts with a phenol to give substituted phenolic compounds with the liberation of hydrogen halide, which in turn reacts with more substituted indene to produce further substituted indene hydrohalide thus perpetuating the reaction.

A further extension is the addition of a small amount of some other hydrocarbon halide to the reaction mass with or without the presence of moisture to initiate the reaction by the liberation of a small amount of hydrogen halide, which in turn reacts with the substituted indene present to form substituted indene hydrohalide, the formation of which is then perpetuated.

The degree of contamination resulting from starting thereaction with a hydrocarbon halide becomes less significant, the larger the quantities of substituted indene hydrohalide and phenol reacted. g l

On the other hand, larger quantities of alkyl or aryl halide maybe employed to initiate the reaction, in which case the product eventually obtained will comprise a mixture of substituted indene, substituted phenols and phenolic ethers, as well as substituted phenols and phenolic ethers derived from the aryl or alkyl halide.

The product thus obtained may be, in turn, reacted as such with an aldehyde to form a resin, or its components may be previously separated such as by fractional distillation at reduced pressures, and then one or more separately reacted with an aldehyde.

The use of a substantial quantity of a hydrocarbon halide other than substituted indene halides permits the preparation of substituted phenols with a wide variety of different properties, since the hydrocarbon halide may be selected from a wide variety of different compounds both alkyl and aryl.

Furthermore, the properties may be varied considerably by varying the relative proportions of hydrocarbon halide and substituted indene hydrohalide.

Substituted indene phenol may be isolated from the reaction mass if desired, by any means known in the art. washing out any excess phenol followed by fractional distillation under reduced pressure.

Substituted indene phenol also may be .isolated directly by fractional distillation under reduced pressure.

When using fractional distillation fairly low pressures are recommended, such as pressures of the order of from 1 to 20 mm. absolute.

For instance, it may be isolated by For example, it may be reacted with iormalde- I hyde or formaldehyde yielding substances, such as hexamethylenetetramine, either with or without the addition of a further coupling agent, for example, a small amount oi oxalic acid.

Usually, it will be found that a further coupling agent is not required since the residual hydrogen halide present in the reaction product serves as a very eflective coupling agent.

The production of phenol-formaldehyde type resins is illustrated by the following examples.

Exmna '7 A 0.5 moi portion of substituted indene phenol was reacted with 0.8 mol of aqueous 38% formaldehyde with good stirring ior a period of 20 hours, using a small amount oi. oxalic acid as a catalyst. The condensation product then was steam distilled.

The resinous product of the substituted phenoliormaldehyde type was obtained in a yield 01.70%. The resin was completely compatible with both as drying oils, linseed oil, tung oil. castor oil, oiticica oil, waxes, such as montan wax: natural resins, such as colophony, kauri, copal, dammar; and synthetic resins, such as coumarone resin, urea-formaldehyde resin and the like.

The resiniflcation reaction may be carried out in two or more stages, if desired.

linseed oil and tung oil as shown in the following example.

' Exlmrtr: 6

A standard gallon varnish was prepared from this resin in the following manner:

Formula Parts Resin 12.2 China-wood oi 14.0 Solvent naphtha V. M. and P 26.2 Drier (cobalt, manganese, and lead drier) 1.0

The mixture of resin and China-wood oil was heated in a copper beaker to a temperature of naphtha. The drier was stirred into the varnish when it reached room temperature.

The product was a clear, light colored varnish with excellent coating properties. It may be used to coat metals, wood, and other surfaces, such as those of beverage and food containers.

The substituted phenolic compounds made in accordance with my invention, may with any of the aldehydes commonly used for the preparation of phenolaldehyde type resins.

In the case of formaldehyde, gaseous formaldehyde, aqueous formaldehyde solutions of diflerent concentrations, polymerization products of formaldehyde, such as trioxymethylene, polyoxymethylenes, or paraformaldehyde, or formaldehyde yielding substances, such as hexamethylene tetramine may be employed.

The resin forming reaction, it desired, may take place in the presence as plasticizers, fillers, and-the like.

Furthermore, the resin-forming reaction may be carried out in the presence of fats; oils such pigments, coloring bodies,

be reacted of inert substances, such Thus, a product may nary condensation reaction and the melting point raised by subsequent heating.

The products resulting from the resinitlcation reaction may vary considerably in their properties, such as from resinous viscous liquids to solid substances of different degrees pending upon the choice of the reactants used ior resiniflcation and resinification conditions such as temperature and reaction time.

As pointed out above, the resins thus produced are ideally suited for incorporation in liquid coating compositions, such as varnishes, lacquers, paints, and the like, in view of their unusual high solubility in the customary drying oils, such as linseed oil and tung oil.

My process is subject to considerable variation.

For instance, the production of substituted indene phenol and the resinification reaction may take place simultaneously, in which case the aidehyde might be added to the reaction mass simultaneously with the other reactants or the aidehyde might be added at any other time or manner, such as at any stage after the reaction for the production of substituted indene phenol has commenced.

This reaction usually does not require a coupling agent. however, a coupling agent may be added. if desired.

Generally speaking, coupling agents suitable for use herein may be of any type and either acid, neutral or alkaline in character.

From the foregoing description and examples, it will be seen that the hydrohalide of substituted indene (which is also referred to for convenience" as substituted indene hydrohallde) may be previously formed or generated in situ. Therefore, for the purposes of the claims, the term substituted indene hydrohalide" unless otherwise modified, is intended to mean a hydrohalide of this character whether previously formed, or formed in situ.

It is to be understood that the above particular description is by way of illustration and that,

. broadly speaking, changes, omissions, additions,

substitutions and/or modifications might be made within the scope of the claims without departing from the spirit of the invention.

I claim:

1. A process for the production of alkyl substituted indene phenol comprising admixing phenol with a relatively small amount of a light oil alkyl substituted indene fraction boiling between C. and 220 C. and a relatively small amount of aluminum chloride, contacting the resulting mixture with a relatively small amount of hydrogen chloride, and adding another but substantial portion of a light oil alkyl substituted indene fraction boiling between 190 C. and 220 C. to said mixture with agitation.

. 2. A process for the production of alkyl substituted indene phenol comprising admixing a phenol with a relatively small amount of a light oil alkyl substituted indene fraction boiling between 190" C. and 220 C. and-a relatively small amount of aluminum chloride, contacting the resuit ng mixture with a relatively small amount be produced by a prelimi-.

of hardness, de-

of hydrogen chloride, and adding another but substantlal portion of a light 011 alkyl substituted indene fraction boiling between 190 C. and 220 C. to said mixture.

FRANK J. SODAY.

REFERENCES .crmn

The following references are of record in the file of this patent:

UNI'JQI'ED STATES PATENTS Number Name Date Phillips Nov. 22, 1927 12 Number Name Date 1,754,052 Rosenthal Apr. 8, 1930 2,171,914 Butler Sept. 5, 1939 2,291,091 Robertson July 28, 1942 5 2,321,440 Ward June 8, 1943 I OTHER REFERENCES Chem. Abst., vol, 23, page 1130, 1929. Abstracting an article of Courlot in Compt. Rend., vol. 187.

Chem. Abst., vol. 32, C01. 5822 (1938). Abstracting an article of Suter in Jour. Am. Chem. Soc. 60, 1365-8 (1938). 

